EP1669415B1 - Farbstoffmischung und deren Verwendung - Google Patents

Farbstoffmischung und deren Verwendung Download PDF

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Publication number
EP1669415B1
EP1669415B1 EP05025981A EP05025981A EP1669415B1 EP 1669415 B1 EP1669415 B1 EP 1669415B1 EP 05025981 A EP05025981 A EP 05025981A EP 05025981 A EP05025981 A EP 05025981A EP 1669415 B1 EP1669415 B1 EP 1669415B1
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EP
European Patent Office
Prior art keywords
formula
dye composition
composition
dye
weight parts
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Not-in-force
Application number
EP05025981A
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English (en)
French (fr)
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EP1669415B2 (de
EP1669415A1 (de
Inventor
Huei-Chin Huang
Sheena Lee
Sheue-Rong Lee
Bao-Kun Lai
Cheng-Hsiang Hsu
Ya-Chi Tseng
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Everlight USA Inc
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Everlight USA Inc
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Priority to PL05025981T priority Critical patent/PL1669415T5/pl
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0055—Mixtures of two or more disazo dyes
    • C09B67/0057—Mixtures of two or more reactive disazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0055—Mixtures of two or more disazo dyes
    • C09B67/0057—Mixtures of two or more reactive disazo dyes
    • C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system

Definitions

  • the present invention relates to dye compositions, and more particularly to black or navy blue reactive dye compositions.
  • the reactive dyestuffs are used for dyeing or printing cellulose fibers or cellulose containing fibers particularly need for high quality such as the properties of leveling, reproducibility, solubility, fastness etc.
  • a novel dye composition with high build-up, and excellent fixation with cellulose as well as able to easily wash off the unfixed dyes is needed.
  • the present invention provides a dye composition comprising of components (A) a disazo dye and (B) a disazo dye.
  • the weight percentage of component (A) ranges from 1-99% and at least one disazo dye is selected from the group consisting of the following formula (I) and (II), wherein
  • the weight percentage of component (B) ranges from 99-1% is a disazo dye of the following formula (III), wherein
  • U can be as follows: -Cl, -Br, -F, -SSO 3 H, -OCO-CH 3 , -OPO 3 H 2 , -OCO-C 6 H 5 , -OSO 2 -C 1-4 alkyl, -OSO 2 -N(C 1-4 alkyl) 2 or
  • V can be as follows: amino, methylamino, ethylamino, ⁇ -sulfoethylamino, o-sulfoaniline, m-sulfoaniline, p-sulfoaniline, 2,4-disulfoaniline, 2,5-disulfoaniline, 1-sulfo-2-naphthylamino, 1,5-disulfo-2- naphthylamino or morpholino.
  • the dye composition of the present invention can further comprise as a dye composition having dyestuffs of formula (I), formula (II) and formula (III) at the same time.
  • the said component (A) includes formula (I) is present in an amount ranging from 10-40% by weight relative to total weight of the composition and formula (II) is present in an amount ranging from 1-20% by weight relative to total weight of the composition.
  • the said component (B) is the formula (III) is present in an amount ranging from 40-89% by weight relative to total weight of the composition.
  • the dye composition of the present invention can be presented in the form of acids or salts, particularly alkaline metallic salt and alkaline-earth metallic salt, application wise preferably is in the form of alkaline metallic salt.
  • the dye composition of the present invention is suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, artificial cotton, linen, and artificial linen, or polyamide fibers, such as wool, silk, and nylon etc. Dyed materials with excellent properties can be obtained, showing especially outstanding performance in build-up, wash off, low nylon stain, and light fastness, and can be used with other dyestuffs as well.
  • the compound of formula (I) of the present invention can be prepared as follows.
  • amino compound of formula (a) undergoes diazotization, afterward it is then coupled with the amino compound of formula (b) below under acidic pH values such as pH of 1-3 at temperatures of 10-20°C, D 1 -NH 2 (a)
  • the compound of formula (I) is the disazo dye of the following formula (Ia): wherein D 1 and D 2 are defined as above. More preferably it is the disazo dye of formula (Ib): wherein (R 3 ) 0-3 and Y are defined as above.
  • formula (I) is formula (2), formula (3), formula (4), formula (5), formula (6) or formula (7):
  • the compound of formula (II) is the disazo dye of formula (IIa): wherein D 1 and D 2 are defined as above. More preferably it is the disazo dye of formula (IIb): wherein (R 3 ) 0-3 and Y are defmed as above.
  • formula (II) is formula (8), formula (9), formula (10), formula (11), formula (12), formula (13) or formula (14):
  • the compound of formula (III) is the disazo dye of formula (IIIa): wherein Q 1 and Q 2 are defined as above. More preferably it is the disazo dye of formula (IIIb): wherein Y is defined as above.
  • the component (A) is present in an amount ranging from 1% to 99% by weight relative to total weight of the composition, and the component (B) is present in an amount ranging from 99% to 1% by weight relative to total weight of the composition.
  • the component (A) is present in an amount ranging from 5% to 95% by weight relative to total weight of the composition, and the component (B) is present in an amount ranging from 95% to 5% by weight relative to total weight of the composition.
  • the component (A) is present in an amount ranging from 10% to 90% by weight relative to total weight of the composition, and the component (B) is present in an amount ranging from 90% to 10% by weight relative to total weight of the composition.
  • composition of the present invention can be further expressed as a composition comprising the formula (I), the formula (II) and the formula (III) at the same time.
  • the said component (A) includes the formula (I) present in an amount ranging from 10% to 40% by weight relative to total weight of the composition and the formula (II) present in an amount ranging from 1% to 20% by weight relative to total weight of the composition.
  • the said component (B) is the formula (III) present in an amount ranging from 40% to 89% by weight relative to total weight of the composition.
  • the said component (A) includes the formula (I) present in an amount ranging from 15% to 40% by weight relative to total weight of the composition and the formula (II) present in an amount ranging form 5% to 20% by weight relative to total weight of the composition, the said component (B) is formula (III) present in an amount ranging from 40% to 80% by weight relative to total weight of the composition.
  • compositions of the present invention can be prepared in several ways.
  • the dye components can be prepared separately and then mixed together to make powder, granular and liquid forms, or a number of individual dyes may be mixed according to the dyeing recipes in a dyehouse.
  • the dye mixtures of the present invention can be prepared, for example, by mixing the individual dyes. The mixing process is carried out, for example, in a suitable mill, such as a ball mill or a pin mill, or kneaders or mixers.
  • the dye composition of the present invention may contain inorganic salts (e.g. sodium chloride, potassium chloride and sodium sulfate), dispersants (e.g. ⁇ - naphthalenesulfonic acid-formaldehyde condensation products, methylnaphthalenesulfonic acid-formaldehyde condensation products, acetylaminonaphthol based compounds, etc.), non-dusting agents (e.g. di-2-ethylhexyl terephthalate, etc.), pH buffering agents (e.g. sodium acetate, sodium phosphate, etc.), water softeners (e.g. polyphosphate, etc.), well-known dyeing assistants, etc.
  • inorganic salts e.g. sodium chloride, potassium chloride and sodium sulfate
  • dispersants e.g. ⁇ - naphthalenesulfonic acid-formaldehyde condensation products, methylnaphthalenesul
  • the form of the dye composition of the present invention is not critical.
  • the dye composition can be powders, granules or liquids form.
  • the compounds are depicted as free acids in the specification.
  • the dyestuffs of the present invention are manufactured, purified or used, they exist in the form of water soluble salts, especially alkaline metallic salts, such as sodium salts, lithium salts, potassium salts or ammonium salts, and preferably sodium salts.
  • the dye compositions of the present invention can be used to dye a wide range of fiber materials, especially for cellulose fiber materials. These dye compositions can also be used to dye natural cellulose fibers and regenerated cellulose fibers, such as cotton, linen, jute, ramie, mucilage rayon, as well as cellulose based fibers.
  • the dyeing by using the dye compositions of the present invention can be any generally used process. Take exhaustion dyeing for example, it utilizes either inorganic neutral salts such as sodium sulfate anhydride and sodium chloride, or acid chelating agents such as sodium carbonate and sodium hydroxide, or both of them.
  • inorganic neutral salts such as sodium sulfate anhydride and sodium chloride
  • acid chelating agents such as sodium carbonate and sodium hydroxide, or both of them.
  • the amount of inorganic neutral salts or base is not of concern, and can be added once or separately. In addition to that, it is optional to add traditionally used dyeing assistants, such as leveling agents and retarding agents.
  • the temperature of dyeing ranges from 40°C to 90°C, and preferably 50°C to 70°C.
  • a cold batch-up dyeing method firstly carried out pad-dyeing by using inorganic neutral salts such as sodium sulfate anhydride and sodium chloride, and acid chelating agents such as sodium silicate and sodium hydroxide, and then the materials were rolled up to start dyeing.
  • inorganic neutral salts such as sodium sulfate anhydride and sodium chloride
  • acid chelating agents such as sodium silicate and sodium hydroxide
  • Continuous dyeing is single batch-up dyeing, which mixes a well-known acid chelating agent such as sodium carbonate or sodium bicarbonate with a pad-dyeing liquor, and pad-dyeing is carried out. After that, the dyed materials are dried or evaporated to fix the color, and then the dyed materials are treated with well-known inorganic neutral salts such as sodium sulfate anhydride and sodium chloride, and acid chelating agents such as sodium hydroxide or sodium silicate. Preferably, the treated materials are dried or evaporated again by common methods to finally fix the color.
  • a well-known acid chelating agent such as sodium carbonate or sodium bicarbonate
  • pad-dyeing liquor pad-dyeing liquor
  • the dyed materials are dried or evaporated to fix the color
  • the dyed materials are treated with well-known inorganic neutral salts such as sodium sulfate anhydride and sodium chloride, and acid chelating agents such as sodium hydroxide or sodium silicate.
  • the treated materials
  • a one-way printing method utilizes a printing paste containing an acid chelating agent such as sodium bicarbonate to print the materials, thereafter the printed materials are dried or evaporated to fix the color.
  • a two-phase printing method includes printing by printing paste and fixing color by soaking the printed materials in high temperature (90°C or above) solution containing inorganic neutral salts (like sodium chloride) and acid chelating agents (like sodium hydroxide or sodium silicate).
  • inorganic neutral salts like sodium chloride
  • acid chelating agents like sodium hydroxide or sodium silicate
  • the dye composition of the present invention has good fixation and excellent build up capacity. Besides, the dye composition exhibits excellent color depth, levelness and wash off properties, as well as high solubility, high exhaustion and high fixation rate. Therefore exhaustion dyeing can be applied under low dyeing temperature and during pad-steaming process only a short steaming time is required for the dye composition.
  • the dyeing results show high fixation yield as well the unfixed regions can be easily washed off, mean while difference between exhaustion yield and fixation yield is small, and only minor unfixed dye losted in cleaning procedure can be detected.
  • the dyeings and prints produced on cellulose fiber materials with the dyestuffs composition according to the present invention have a good depth of color and a high fiber-dyestuff bonding stability both in the acid and in the alkaline range.
  • the dyed cellulose fiber materials have excellent properties of light fastness, wet-light fastness, and wet fastness, e.g. wash fastness, water fastness, seawater fastness, cross-dyeing fastness, and perspiration fastness, as well as wrinkling fastness, ironing fastness, and rubbing fastness. Therefore, the present invention is a valuable reactive black dye for cellulose fibers in the present dyeing industry.
  • the dye compositions have the materials dyed with excellent properties and resulting outstanding build-up and light fastness.
  • Preparation example 2 33.8 parts of 1-aminobenzene-4- ⁇ -sulfatoethylsulfone are prepared and dissolved in 200 parts of ice water, and followed by stirring in 16 parts of 32% HCl aqueous solution. Subsequently the reacting solution undergoes diazotization by the addition of 8.7 parts of sodium nitrite aqueous solution under a temperature of 0 to 5°C. To this mixture 9.1 parts of powdered 3,5-diaminobenzoic acid are then added, and the pH is adjusted gradually to 3.5 by the addition of sodium bicarbonate. Under a temperature of 10-15°C, it is stirred till coupling reaction has completed. The solution is salted out with NaCl and filtered to obtain compound (3).
  • the reactive dyestuffs described below can be prepared, and upon dyeing with specific dyestuffs, dyed cotton fiber demonstrates excellent fastness properties.
  • Preparing dyestuffs of formula (15) and formula (2) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (2) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (2) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (2) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (3) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (3) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (3) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (3) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (4) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (4) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (5) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (5) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (7) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (7) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (7) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (7) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (8) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (8) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (9) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (9) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (9) as described above Take 75 weight parts of formula (15) and 25 weight parts of formula (9) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (9) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (9) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (10) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (10) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (10) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (10) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (11) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (11) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (11) as described above Take 60 weight parts of formula (15) and 40 weight parts of formula (11) and mixed completely to form a dye composition.
  • Preparing dyestuffs of formula (15) and formula (12) as described above Take 90 weight parts of formula (15) and 10 weight parts of formula (12) and mixed completely to form a dye composition.
  • the colored fabric was placed in an oven at 65°C to dry for 5 minutes then taken out, and put into a steam oven using saturated steam for 10 minutes at 102-105°C.
  • the colored fabric was washed with cold water, hot water, and soap then dried to obtain a black fabric with good dyeing properties.
  • dyestuff prepared as in example 3 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber's salt, 2.4 parts, and 32% sodium carbonate solution, 2.5 parts. The dyeing bottle was shaken at 60°C for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a black fabric with good dyeing properties.
  • the dye compositions of the present invention are suitable for common uses and have excellent dyeing properties. They can be used to dye cellulose fibers with various dyeing methods, such as exhaustion dyeing, printing-dyeing, or continuous dyeing that are commonly used in reactive dyestuffs.
  • the dye compositions of the present invention are water-soluble dyestuffs that have a highly commercial value.
  • the dye compositions of the present invention can obtain dyeing results with excellent properties in all aspects, especially in washing off, build-up, levelness, low nylon stain, light fastness, and wet-light fastness.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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Claims (19)

  1. Farbstoffzusammensetzung, umfassend:
    (A) mindestens einen Bisazofarbstoff, ausgewählt aus der Formel (I) oder (II), der in einer Menge im Bereich von 1 bis 99 Gew.-% vorliegt,
    Figure imgb0078
    Figure imgb0079
     wobei
    R Wasserstoff oder Carboxy ist;
    R1 und R2 jeweils unabhängig voneinander Wasserstoff oder C1-4-Alkyl bedeuten;
    D1 und D2 jeweils unabhängig eine beliebige Gruppe sein können, die ausgewählt ist aus den nachstehenden (1a), (1b), (1c), (1d) oder (1e)
    Figure imgb0080
    Figure imgb0081
    Figure imgb0082
    Figure imgb0083
    Figure imgb0084
     wobei (R3)0-3 und (R4)0-3 jeweils unabhängig voneinander 0 bis 3 identische oder unterschiedliche Reste sind, die ausgewählt sind aus der Gruppe, bestehend aus Halogen, Carboxy, Sulfo, C1-4-Alkyl und C1-4-Alkoxy;
    R5 Wasserstoff oder C1-4-Alkyl ist, das unsubstituiert oder durch Hydroxy, Sulfo, Carboxy oder Cyano substituiert ist;
    (R6)0-2 0 bis 2 identische oder unterschiedliche Reste ist, die ausgewählt sind aus der Gruppe, bestehend aus Sulfo, C1-4-Alkyl und C1-4-Alkoxy;
    R7 Wasserstoff, Sulfo, C1-4-Alkyl oder C1-4-Alkoxy ist;
    R8 Wasserstoff, Ureido, Sulfo, C1-4-Alkyl, C1-4-Alkoxy oder C2-4-Alkanoylamino ist;
    V Amino ist, das unsubstituiert oder durch nichtfaserreaktive Reste substituiert ist;
    Q und Q' jeweils unabhängig voneinander -NH-CO-CH(Hal)-CH2(Hal), - NH-CO-C(Hal)=CH2 oder -SO2-Y bedeuten;
    Y -CH=CH2, -CH2CH2OSO3H oder -CH2CH2-U ist; U eine Gruppe ist, die unter alkalischen Bedingungen eliminiert werden kann;
    Hal Halogen ist;
    m eine ganze Zahl von 0 oder 1 ist; und
    (B) einen Bisazofarbstoff der Formel (III), der in einer Menge im Bereich von 99 bis 1 Gew.-% vorliegt,
    Figure imgb0085
     wobei (R9)0-2 und (R10)0-2 jeweils unabhängig voneinander 0 bis 2 identische oder unterschiedliche Reste sind, die ausgewählt sind aus der Gruppe, bestehend aus Sulfo, C1-4-Alkyl und C1-4-Alkoxy;
    Q1 und Q2 jeweils unabhängig voneinander -NH-CO-CH(Hal)-CH2(Hal), - NH-CO-C(Hal)=CH2 oder -SO2-Y bedeuten;
    Y -CH=CH2, -CH2CH2OSO3H oder -CH2CH2-U ist; U eine Gruppe ist, die unter alkalischen Bedingungen eliminiert werden kann;
    Hal Halogen ist.
  2. Farbstoffzusammensetzung nach Anspruch 1, wobei in dem Bisazofarbstoff der Formel (I) oder (II) von Bestandteil (A) die Substituentengruppen D1 und D2 die Formel (1a) oder (1c) aufweisen.
  3. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (I) die Formel (Ia) ist:
    Figure imgb0086
     wobei D1 und D2 dieselben wie in Anspruch 1 definiert sind.
  4. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (II) die Formel (IIa) ist:
    Figure imgb0087
     wobei D1 und D2 dieselben wie in Anspruch 1 definiert sind.
  5. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (III) die Formel (IIIa) ist:
    Figure imgb0088
     wobei Q1 und Q2 dieselben wie in Anspruch 1 definiert sind.
  6. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (I) die Formel (Ib) ist:
    Figure imgb0089
     wobei (R3)0-3 und Y dieselben wie in Anspruch 1 definiert sind.
  7. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (II) die Formel (IIb) ist:
    Figure imgb0090
     wobei (R3)0-3 und Y dieselben wie in Anspruch 1 definiert sind.
  8. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (III) die Formel (IIIb) ist:
    Figure imgb0091
     wobei Y dasselbe wie in Anspruch 1 definiert ist.
  9. Farbstoffzusammensetzung nach Anspruch 6, wobei die Formel (Ib) die Formel (2) ist:
    Figure imgb0092
  10. Farbstoffzusammensetzung nach Anspruch 6, wobei die Formel (Ib) die Formel (3) ist:
    Figure imgb0093
  11. Farbstoffzusammensetzung nach Anspruch 7, wobei die Formel (IIb) die Formel (8) ist:
    Figure imgb0094
  12. Farbstoffzusammensetzung nach Anspruch 7, wobei die Formel (IIb) die Formel (9) ist:
    Figure imgb0095
  13. Farbstoffzusammensetzung nach Anspruch 7, wobei die Formel (IIb) die Formel (10) ist:
    Figure imgb0096
  14. Farbstoffzusammensetzung nach Anspruch 7, wobei die Formel (IIb) die Formel (11) ist:
    Figure imgb0097
  15. Farbstoffzusammensetzung nach Anspruch 8, wobei die Formel (IIIb) die Formel (15) ist:
    Figure imgb0098
  16. Farbstoffzusammensetzung nach Anspruch 1, wobei die Formel (I) die Formel (16) ist:
    Figure imgb0099
  17. Farbstoffzusammensetzung nach Anspruch 1, wobei der Bestandteil (A) in einer Menge im Bereich von 5 bis 95 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt und der Bestandteil (B) in einer Menge im Bereich von 95 bis 5 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt.
  18. Farbstoffzusammensetzung nach Anspruch 1, wobei der Bestandteil (A) Formel (I), die in einer Menge im Bereich von 10 bis 40 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt, und Formel (II), die in einer Menge im Bereich von 1 bis 20 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt, einschließt und der Bestandteil (B) Formel (III) ist, die in einer Menge im Bereich von 40 bis 89 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt.
  19. Farbstoffzusammensetzung nach Anspruch 18, wobei die Formel (I) in einer Menge im Bereich von 15 bis 40 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt, Formel (II) in einer Menge im Bereich von 5 bis 20 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt und Formel (III) in einer Menge im Bereich von 40 bis 80 Gew.-% in Bezug auf das Gesamtgewicht der Zusammensetzung vorliegt.
EP05025981.1A 2004-11-29 2005-11-29 Farbstoffmischung und deren Verwendung Not-in-force EP1669415B2 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898869A (zh) * 2012-09-28 2013-01-30 浙江亿得化工有限公司 一种复合深黑色活性染料

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100413930C (zh) * 2005-08-31 2008-08-27 明德国际仓储贸易(上海)有限公司 反应性染料组成物及其应用
CN100413927C (zh) * 2005-09-05 2008-08-27 明德国际仓储贸易(上海)有限公司 双偶氮染料化合物及其应用
DE102005047391A1 (de) * 2005-10-05 2007-04-12 Dystar Textilfarben Gmbh & Co. Deutschland Kg Farbstoffe und Farbstoffmischungen von faserreaktiven Azofarbstoffen, ihre Herstellung und ihre Verwendung
CN101195715A (zh) * 2006-12-05 2008-06-11 明德国际仓储贸易(上海)有限公司 反应性红色染料组成物及其应用
DE102008054404A1 (de) * 2008-12-09 2010-06-10 Dystar Textilfarben Gmbh & Co. Deutschland Kg Faserreaktive Azofarbstoffe und Farbstoffmischungen, Verfahren zu ihrer Herstellung und ihre Verwendung
US8349029B2 (en) 2008-12-09 2013-01-08 Dystar Colours Deutschland Gmbh Fiber-reactive azo dyes and dye mixtures, preparation thereof and use thereof
CN101580649B (zh) * 2009-06-11 2012-12-12 湖北华丽染料工业有限公司 一种复合活性黑染料
CN102558907B (zh) * 2011-12-30 2014-07-09 浙江科永化工有限公司 一种复合活性黑染料组合物
EP2912118B1 (de) 2012-10-25 2016-09-07 DyStar Colours Distribution GmbH Mischungen aus faserreaktiven azo-farbstoffen, herstellung und verwendung
EP2725070A1 (de) 2012-10-25 2014-04-30 DyStar Colours Distribution GmbH Mischungen aus faserreaktiven Azo-Farbstoffen, Herstellung und Verwendung
ES2618019T3 (es) 2012-10-25 2017-06-20 Dystar Colours Distribution Gmbh Mezclas de colorantes azoicos reactivos con las fibras, su preparación y su uso
EP2725069A1 (de) 2012-10-25 2014-04-30 DyStar Colours Distribution GmbH Mischungen aus faserreaktiven Azo-Farbstoffen, Herstellung und Verwendung
EP2725068A1 (de) 2012-10-25 2014-04-30 DyStar Colours Distribution GmbH Mischungen von faserreaktiven Azo-Farbstoffen, Herstellung und Verwendung
CN103351644A (zh) * 2013-07-09 2013-10-16 沈钢 一种高性能多偶氮棕色活性染料及其混合物的合成与应用
CN107501995A (zh) * 2017-07-28 2017-12-22 浙江科永化工有限公司 一种橙色活性染料化合物及其制备方法和应用
CN109294276A (zh) * 2018-11-09 2019-02-01 上海贝通色彩科技有限公司 一种活性染料的组合物及其制备方法和用途
CN111073341A (zh) * 2019-12-23 2020-04-28 湖北丽源科技股份有限公司 一种黑色活性复合染料及其制备工艺和应用
CN111593586A (zh) * 2020-05-07 2020-08-28 宁波大千纺织品有限公司 一种高耐水洗牢度吸水速干尼龙-棉交织针织物的染色工艺

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063468C (zh) * 1996-05-08 2001-03-21 台湾永光化学工业股份有限公司 黑色染料组合物
DE19635999A1 (de) * 1996-09-05 1998-03-12 Dystar Textilfarben Gmbh & Co Farbstoffmischungen von faserreaktiven Azofarbstoffen und ihre Verwendung zum Färben von hydroxy- und/oder carbonamidgruppenhaltigem Fasermaterial
SG68660A1 (en) * 1997-04-07 1999-11-16 Ciba Sc Holding Ag Mixtures of reactive dyes and their use
TW466263B (en) * 1998-07-28 2001-12-01 Dystar Textilfarben Gmbh & Amp Fiber-reactive black dye mixtures and use thereof for dyeing hydroxy-and/or carboxamido-containing fiber material
US6171349B1 (en) * 1999-01-20 2001-01-09 Everlight Usa, Inc. Reactive dye composition
TWI231820B (en) † 1999-03-11 2005-05-01 Ciba Sc Holding Ag Azo dyes, their preparation and their use
US6790411B1 (en) * 1999-12-02 2004-09-14 3M Innovative Properties Company Hydrogen peroxide indicator and method
DE10212770A1 (de) * 2002-03-22 2003-10-02 Dystar Textilfarben Gmbh & Co Farbstoffmischungen von faserreaktiven Azofarbstoffen und ihre Verwendung
DE10217478A1 (de) * 2002-04-19 2003-11-06 Dystar Textilfarben Gmbh & Co Farbstoffmischungen von faserreaktiven Azofarbstoffen, ihre Herstellung und ihre Verwendung
MY136589A (en) † 2003-02-05 2008-10-31 Ciba Sc Holding Ag Mixtures of reactive dyes and their use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898869A (zh) * 2012-09-28 2013-01-30 浙江亿得化工有限公司 一种复合深黑色活性染料

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CN1781996A (zh) 2006-06-07
ES2359315T5 (es) 2017-08-02
DE602005025727D1 (de) 2011-02-17
PL1669415T3 (pl) 2011-06-30
ATE494335T1 (de) 2011-01-15
US20060112504A1 (en) 2006-06-01
ES2359315T3 (es) 2011-05-20
EP1669415B2 (de) 2017-03-22
EP1669415A1 (de) 2006-06-14
CN100368483C (zh) 2008-02-13
US7387647B2 (en) 2008-06-17
PL1669415T5 (pl) 2017-10-31

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